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CN114017993B - 一种利用绿电电解水制氢副产氧气的装置及方法 - Google Patents

一种利用绿电电解水制氢副产氧气的装置及方法 Download PDF

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Publication number
CN114017993B
CN114017993B CN202210008248.7A CN202210008248A CN114017993B CN 114017993 B CN114017993 B CN 114017993B CN 202210008248 A CN202210008248 A CN 202210008248A CN 114017993 B CN114017993 B CN 114017993B
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oxygen
heat exchanger
liquid oxygen
pressurized
channel
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CN114017993A (zh
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韩一松
谭芳
彭旭东
劳利建
李玲
姚蕾
任美凤
徐申骏
谢小雨
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Hang Yang Group Co ltd
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Hang Yang Group Co ltd
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Priority to FR2300139A priority patent/FR3131588A1/fr
Priority to DE102023100232.5A priority patent/DE102023100232A1/de
Priority to US18/150,214 priority patent/US20230212768A1/en
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    • C—CHEMISTRY; METALLURGY
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    • F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

一种利用绿电电解水制氢副产氧气的装置及方法,用于降低空分设备规模，降低空压机的处理气量，减少空分设备投资，减少运行能耗,本发明所述装置包括：氧气纯化系统、换热系统、空分压缩及膨胀系统、空分精馏系统、液氧存储系统，本发明首先对绿电电解水制得的氧气进行纯化净化以除去氧气中的氢气、一氧化碳、二氧化碳、水等杂质，然后将纯净氧气送入换热系统中进行换热液化，得到液氧并耦合空分精馏系统精馏产生的液氧，通过换热系统和空分压缩及膨胀系统获得带压氧气。本发明系统间高度耦合，有效降低了空压机的负荷，降低了空分设备规模，减少了空分设备运行能耗，实现了高效安全节能的目的。

Description

一种利用绿电电解水制氢副产氧气的装置及方法
技术领域
本发明涉及太阳能等可再生能源生成的绿电水电解制氢副产氧气与空分设备内压缩制氧耦合利用，氧液化储能利用，具体涉及一种利用绿电电解水制氢副产氧气的装置及方法，属于制氧技术领域和储能技术领域。
背景技术
氢能由于其在释放过程中的零碳排放，在改变人类能源体系方面被寄予了厚望。而利用太阳能等可再生能源发电水电解所制得的“绿氢”，由于其制备过程中没有碳排放，被认为是氢能利用的理想形态。
中国油气匮乏，煤炭相对丰富的资源特点，现代煤化工可实现石油和天然气资源的补充和部分替代。但煤化工需要大量稳定供给的高压氧气，如400万吨/年煤间接液化制油项目需要至少100万标方/小时的高压氧气。利用深冷法空分设备生产高压氧气和液氧是目前市场最经济的方法，即便如此，根据NB/T 10429-2020《煤化工空气分离设备能效计算方法》表2基准当量单位制氧能耗取值中氧气压力在5.0MPaG的当量制氧单耗在0.658-0.677 KW.h/m3之间，如何有效降低煤化工需要氧气的单耗问题是目前行业亟需解决的问题。
太阳能等绿色能源，因受自然环境因素（季节、天气）的影响极大，其发电过程具有波动大、间断性、随机性、不可控等特点，易导致绿电水电解随环境因素负荷变化大；另一方面，大规模绿电水电解制氢副产的氧气目前并没有得到很好的利用，存在大量的弃氧现象发生。
发明内容
本发明要解决的技术问题是：提供一种利用绿电电解水制氢副产氧气的装置及方法，通过与空分设备耦合，结合液氧储能的形式，高效安全的回收利用绿电电解水制氢副产的氧气，从而降低空分设备规模，降低空压机的处理气量，减少空分设备投资，减少运行能耗，降低用户的整体碳排放，实现高效节能的目的，为实现上述目的，本发明采用的如下技术：一种利用绿电电解水制氢副产氧气的装置，其特征在于所述装置包括氧气纯化系统、换热系统、空分压缩及膨胀系统、空分精馏系统、液氧存储系统；相互之间通过管道连接，所述氧气纯化系统包括氧自过热器，氧加热器，氧气净化器，冷水机组、冷水机组，氧气纯化器，其中氧自过热器的氧气输入端连接于电解水制氢系统的氧气输出端，氧自过热器的氧气输出端连接于氧加热器的氧气输入端，氧加热器的氧气输出端连接于氧气净化器的氧气输入端，氧气净化器的净化氧气输出端连接于冷水机组和冷水机组的氧气输入端，冷水机组和冷水机组的氧气输出端连接于氧气纯化器的氧气输入端，氧气纯化器输出端纯化后氧气通过管道送入换热系统，所述换热系统包括换热器和过冷器，所述液氧存储系统包括液氧贮槽，所述空分压缩及膨胀系统包括增压机，用于获得压缩气体；至少一台膨胀机，该膨胀机含膨胀机增压端、冷却器、膨胀机膨胀端；流程液氧泵和液氧增压泵，所述液氧存储系统的输出端连接于液氧增压泵的输入端，液氧增压泵的输出端连接于流程液氧泵的输入端。
作为优选：所述换热系统及空分压缩及膨胀系统与空分精馏系统高度耦合，其中所述换热器设置至少四个正流通道和二个通道，四个正流通道分别为纯化后氧气通道、带压空气通道、增压后气体通道和增压膨胀气体通道，二个返流通道分别为高压氧气产品通道、返流气体通道，所述换热器的纯化后氧气通道输入端连接于氧气纯化器的氧气输出端，换热器的纯化后氧气通道输出端连接于阀的输入端，阀的输出端连接于过冷器的热流体输入端，过冷器的热流体输出端的液氧经阀门和管道连接于液氧存储系统的输入端。换热器的带压空气通道输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，换热器的带压空气通道输出端连接于空分精馏系统。换热器的增压后气体通道输入端连接于增压机的末级输出端，换热器的增压后气体通道输出端连接于节流阀的输入端；换热器的增压膨胀气体通道输入端连接于膨胀机增压端后冷却器输出端，换热器的增压膨胀气体通道输出端连接于膨胀机膨胀端的输入端，膨胀机膨胀端的输出端连接于空分精馏系统；换热器的高压氧气产品通道输入端连接于流程液氧泵的输出端，换热器的高压氧气产品通道输出端连接于高压氧气产品输出管道；换热器的返流通道输入端连接于过冷器的冷流体输出端，换热器的返流通道输出端连接于空分设备后续工艺，过冷器的冷流体输入端连接于空分精馏系统。所述增压机的输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，增压机的一段输出端连接于膨胀机增压端的输入端。
作为优选：所述空分精馏系统至少包括二个输入通道和二个输出通道，其中二个输入通道分别为高压气体节流输入通道、带压气体输入通道；二个输出通道分别为返流气体输出通道、流程液氧输出通道，该高压气体节流输入通道输入端连接于节流阀的输出端，带压气体输入通道输入端连接于换热器的带压空气通道输出端；返流气体输出通道连接于过冷器的冷流体输入端，流程液氧输出通道连接于阀的输出端，并连接于流程液氧泵的输入端。
作为优选：所述换热器在绿电充足时，该净化氧气送入换热器中进行换热液化后得到液氧，此液氧经阀后部分液氧耦合空分精馏系统精馏产生的液氧进入液程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气，其余部分液氧经过冷器过冷后进入液氧贮槽，当换热器在绿电不充足时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧和与净化氧气送入换热器中进行换热液化后得到的全部液氧一起进入流程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气，当换热器在绿电不工作时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧一起进入流程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气。
作为优选：所述换热器为板翅式换热器。
一种利用绿电电解水制氢副产氧气装置的使用方法，包括以下步骤：
步骤1：出绿色电解水制氢装置的副产氧气进入到氧自过热器中，被预加热至一定温度，当温度满足进入氧纯化器时，通过管道直接进入到氧纯化器中，当氧自过热温度不满足进入氧纯化器的要求时，则先进入氧加热器进行加热，加热后进入到氧纯化器中；加热后的氧气在氧纯化器中发生化学反应，将氧气中的杂质H2转化为H2O，CO转化为CO2；反应结束后的氧气进入到氧自过热器的热端，与出电解水制氢装置的副产氧气进行热交换降温，并通过经冷却机组冷却后继续降温，在此过程中将底部冷凝下来的水直接排空，冷却后的气体进入到氧净化器中除去氧气中的杂质；
步骤2：净化后的氧气进入到换热器中，在换热器中与返流气体和流程流氧进行换热，使净化氧气被冷却到液态，经阀后得到液氧。在绿电充足时，这部分液氧分为两股，其中一股液氧与从空分精馏系统精馏产生的液氧汇合进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。另一股液氧经过冷器过冷后进入液氧贮槽贮存备用。在绿电不充足时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧和与净化氧气送入换热器中进行换热液化后得到的阀后的全部液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。在绿电不工作时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。
步骤3：经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气的部分或全部进入增压机压缩，增压后一部分增压空气进入膨胀机增压端增压，增压后进入冷却器冷却后进入换热器；增压后另一部分直接进入换热器。进入换热器增压膨胀气体通道的空气从换热器中部抽出后进入膨胀机膨胀端膨胀，膨胀后进入空分精馏系统参与精馏。进入换热器增压后气体通道的空气被返流的流程液氧和从空分精馏系统中来的返流气体换热，冷却后从换热器底部抽出，经节流降压后进入空分精馏系统参与精馏。经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气也可部分进入换热器的带压空气通道，被换热冷却后从换热器底部抽出，进入空分精馏系统参与精馏。
作为优选：所述氧纯化器中使用的催化剂活性组分为钯、铂、铈金属及其氧化物中的一种或几种。
作为优选：所述氧净化器中使用的净化剂为氧化铝和分子筛；其催化剂的填装方式为规整填料。
本发明具有的有益效果如下：
本发明利用太阳能等可再生能源生成的绿电水电解制氢副产氧气与空分设备内压缩制氧耦合利用，当绿电充足时，水电解制氢副产氧气经纯化后进行换热液化后得到液氧，一部分液氧与空分设备空分精馏系统精馏产生的液氧一起加压汽化复热，获得带压氧气供用户，剩余液氧经过冷后贮存备用于液氧贮槽。当绿电不充足时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧及水电解制氢副产氧气经纯化后进行换热液化后得到的全部液氧一起进入流程液氧泵加压汽化后得热，获得带压氧气。当绿电不工作时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧一起进入流程液氧泵加压汽化后得热，获得带压氧气。
本发明一方面解决了绿电水电解制氢副产氧气的浪费问题，另一方面解决了光电资源不连续生成的绿电水电解制氢副产氧气的不稳定与空分设备内压缩制氧稳定性需求的矛盾难题，通过两者耦合利用与通过液氧储能的形式，可实现最大限度的利用光电等可再生能源，在保证用户用氧气量的同时，降低了空分设备规模，有效降低了空压机的负荷，减少了空分设备运行能耗，实现了高效安全节能的目的。同时降低了碳排放，实现了企业经济效益和环境效益的双赢，具有良好的推广前景。
附图说明
图1是本发明的示意图。
图2是本发明一种变形实例示意图。
具体实施方式
为使本发明需解决的技术问题、技术方案和有益效果更加清楚，下面结合附图和具体实施方式对本发明作进一步详细说明，如图1所示：一种利用绿电电解水制氢副产氧气的装置，所述装置包括氧气纯化系统、换热系统、空分压缩及膨胀系统、空分精馏系统、液氧存储系统；相互之间通过管道连接，所述氧气纯化系统包括氧自过热器1，氧加热器2，氧气净化器3，冷水机组4、冷水机组5，氧气纯化器6，其中氧自过热器1的氧气输入端连接于电解水制氢系统的氧气输出端，氧自过热器1的氧气输出端连接于氧加热器2的氧气输入端，氧加热器2的氧气输出端连接于氧气净化器3的氧气输入端，氧气净化器的净化氧气输出端连接于冷水机组4和冷水机组5的氧气输入端，冷水机组4和冷水机组5的氧气输出端连接于氧气纯化器6的氧气输入端，氧气纯化器6输出端纯化后氧气通过管道送入换热系统，所述换热系统包括换热器7和过冷器8，所述液氧存储系统包括液氧贮槽10，所述空分压缩及膨胀系统包括增压机11，用于获得压缩气体；至少一台膨胀机，该膨胀机含膨胀机增压端12A、冷却器13、膨胀机膨胀端12B；流程液氧泵15和液氧增压泵14，所述液氧存储系统的输出端连接于液氧增压泵14的输入端，液氧增压泵14的输出端连接于流程液氧泵15的输入端，所述换热系统及空分压缩及膨胀系统与空分精馏系统高度耦合，其中所述换热器7设置至少四个正流通道和二个通道，四个正流通道分别为纯化后氧气通道、带压空气通道、增压后气体通道和增压膨胀气体通道，二个返流通道分别为高压氧气产品通道、返流气体通道，所述换热器7的纯化后氧气通道输入端连接于氧气纯化器6的氧气输出端，换热器7的纯化后氧气通道输出端连接于阀V02的输入端，阀V02的输出端连接于过冷器8的热流体输入端，过冷器8的热流体输出端的液氧经阀门和管道连接于液氧存储系统的输入端。换热器7的带压空气通道输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，换热器7的带压空气通道输出端连接于空分精馏系统。换热器7的增压后气体通道输入端连接于增压机的末级输出端，换热器7的增压后气体通道输出端连接于节流阀V01的输入端；换热器7的增压膨胀气体通道输入端连接于膨胀机增压端12A后冷却器13输出端，换热器7的增压膨胀气体通道输出端连接于膨胀机膨胀端12B的输入端，膨胀机膨胀端12B的输出端连接于空分精馏系统；换热器7的高压氧气产品通道输入端连接于流程液氧泵15的输出端，换热器7的高压氧气产品通道输出端连接于高压氧气产品输出管道；换热器7的返流通道输入端连接于过冷器8的冷流体输出端，换热器7的返流通道输出端连接于空分设备后续工艺，过冷器8的冷流体输入端连接于空分精馏系统。所述增压机11的输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，增压机11的一段输出端连接于膨胀机增压端12A的输入端，所述空分精馏系统9至少包括二个输入通道和二个输出通道，其中二个输入通道分别为高压气体节流输入通道、带压气体输入通道；二个输出通道分别为返流气体输出通道、流程液氧输出通道，该高压气体节流输入通道输入端连接于节流阀V01的输出端，带压气体输入通道输入端连接于换热器7的带压空气通道输出端；返流气体输出通道连接于过冷器8的冷流体输入端，流程液氧输出通道连接于阀V02的输出端，并连接于流程液氧泵15的输入端，所述换热器7在绿电充足时，该净化氧气送入换热器7中进行换热液化后得到液氧，此液氧经阀V02后部分液氧耦合空分精馏系统9精馏产生的液氧进入液程液氧泵15加压后，通过换热器7和空分压缩及膨胀系统获得带压氧气，其余部分液氧经过冷器8过冷后进入液氧贮槽10，当换热器7在绿电不充足时，液氧贮槽10中的液氧经液氧增压泵14增压后，与从空分精馏系统9精馏产生的液氧和与净化氧气送入换热器7中进行换热液化后得到的全部液氧一起进入流程液氧泵15加压后，通过换热器7和空分压缩及膨胀系统获得带压氧气，当换热器7在绿电不工作时，液氧贮槽10中的液氧经液氧增压泵14增压后，与从空分精馏系统9精馏产生的液氧一起进入流程液氧泵15加压后，通过换热器7和空分压缩及膨胀系统获得带压氧气，所述换热器7为板翅式换热器。
一种利用绿电电解水制氢副产氧气装置的使用方法，包括以下步骤：
步骤1：出绿色电解水制氢装置的副产氧气进入到氧自过热器中，被预加热至一定温度，当温度满足进入氧纯化器时，通过管道直接进入到氧纯化器中，当氧自过热温度不满足进入氧纯化器的要求时，则先进入氧加热器进行加热，加热后进入到氧纯化器中；加热后的氧气在氧纯化器中发生化学反应，将氧气中的杂质H2转化为H2O，CO转化为CO2；反应结束后的氧气进入到氧自过热器的热端，与出电解水制氢装置的副产氧气进行热交换降温，并通过经冷却机组冷却后继续降温，在此过程中将底部冷凝下来的水直接排空，冷却后的气体进入到氧净化器中除去氧气中的杂质；
步骤2：净化后的氧气进入到换热器中，在换热器中与返流气体和流程流氧进行换热，使净化氧气被冷却到液态，经阀后得到液氧。在绿电充足时，这部分液氧分为两股，其中一股液氧与从空分精馏系统精馏产生的液氧汇合进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。另一股液氧经过冷器过冷后进入液氧贮槽贮存备用。在绿电不充足时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧和与净化氧气送入换热器7中进行换热液化后得到的阀V02后的全部液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。在绿电不工作时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，得到带压氧气。
步骤3：经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气的部分或全部进入增压机压缩，增压后一部分增压空气进入膨胀机增压端增压，增压后进入冷却器冷却后进入换热器；增压后另一部分直接进入换热器。进入换热器增压膨胀气体通道的空气从换热器中部抽出后进入膨胀机膨胀端膨胀，膨胀后进入空分精馏系统参与精馏。进入换热器增压后气体通道的空气被返流的流程液氧和从空分精馏系统中来的返流气体换热，冷却后从换热器底部抽出，经节流降压后进入空分精馏系统参与精馏。经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气也可部分进入换热器的带压空气通道，被换热冷却后从换热器底部抽出，进入空分精馏系统参与精馏，所述氧纯化器中使用的催化剂活性组分为钯、铂、铈金属及其氧化物中的一种或几种，所述氧净化器中使用的净化剂为氧化铝和分子筛；其催化剂的填装方式为规整填料。
具体实施例：
如图1所示：出绿色电解水制氢装置的压力约为1.0MPa副产氧气在氧纯化器3中发生化学反应，将氧气中的杂质H2转化为H2O，CO转化为CO2；然后在氧净化器6中除去氧气中的杂质，出氧气净化器6后的氧气中CO2和H2O含量不大于1ppm；净化后的氧气进入到换热器7中，在换热器7中与返流气体和流程流氧进行换热，使净化氧气被冷却到液态，经阀V02节流到0.5MPa后得到液氧。在绿电充足时，这部分液氧分为两股，其中一股液氧与从空分精馏系统精馏产生的液氧汇合进入流程液氧泵15加压到约5.6MPa，加压后进入换热器7，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行换热汽化，出换热器７后得到压力约为5.5MPa的氧气供应用户。阀V02节流后的另一股0.5MPa液氧经过冷器过冷到约81K后进入液氧贮槽贮存备用。在绿电不充足时，贮存在液氧贮槽中的液氧经液氧增压泵14增压到约0.5MPa后，补充从空分精馏系统9精馏产生的液氧和与净化氧气送入换热器7中进行换热液化后得到的阀V02后的全部液氧，一起进入流程液氧泵15加压到约5.6MPa，加压后进入换热器7，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，出换热器7后得到压力约为5.5MPa的氧气。在绿电不工作时，贮存在液氧贮槽中的液氧经液氧增压泵14增压到约0.5MPa后，补充从空分精馏系统9精馏产生的液氧，一起进入流程液氧泵15加压到约5.6MPa，加压后进入换热器7，与纯化后氧气、增压后气体和增压膨胀气体等正流体进行汽化复热，出换热器7后得到压力约为5.5MPa的氧气。增压泵的增压和阀V02调节的目的是为了调压，使得进入流程液氧泵的不同来源液氧压力保持一致。经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气的部分进入增压机压缩，增压后一部分压力约为3.0MPa的空气进入膨胀机增压端12A增压到约4.5MPa，增压后进入冷却器13冷却到约40℃后进入换热器7的增压膨胀气体通道，并从换热器7中部抽出后进入膨胀机膨胀端12B膨胀到约0.5MPa，膨胀后进入空分精馏系统参与精馏。增压后另一部分压力约为7.5MPa的空气直接进入换热器7的增压后气体通道，被返流的流程液氧和从空分精馏系统中来的返流气体换热，冷却后从换热器7底部抽出，经节流降压到约0.5MPa后进入空分精馏系统参与精馏。经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气其余部分直接进入换热器7的带压空气通道，被换热冷却到约100K后从换热器7底部抽出，进入空分精馏系统参与精馏。
附图2所示为增压机11采用一段式的一种高效安全的回收利用绿电电解水制氢副产氧气耦合空分设备内压缩制氧能力的装置。
经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气的部分空气进入增压机11统一压缩到约5.0MPa后出增压机11，一部分增压空气进入膨胀机增压端12A继续增压到约7.5MPa，增压后进入冷却器13冷却到约40℃后进入换热器7的增压后气体通道，被返流的流程液氧和从空分精馏系统中来的返流气体换热，冷却后从换热器7底部抽出，经节流降压到约0.5MPa后进入空分精馏系统参与精馏。一部分增压空气直接进入增压膨胀气体通道，并从换热器7中部抽出后进入膨胀机膨胀端12B膨胀到约0.5MPa，膨胀后进入空分精馏系统参与精馏。经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气其余部分直接进入换热器7的带压空气通道，被换热冷却到约100K后从换热器7底部抽出，进入空分精馏系统参与精馏。
应当指出，由于常规的空分设备内压缩制氧流程形式多样,本发明不限于以上实施例，还可以有很多变形。对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进、修饰及变形，这些改进、修饰和变形也落入本发明权利要求的保护范围内。

Claims (7)

1.一种利用绿电电解水制氢副产氧气的装置，其特征在于：所述装置包括氧气纯化系统、换热系统、空分压缩及膨胀系统、空分精馏系统、液氧存储系统；相互之间通过管道连接，所述氧气纯化系统包括氧自过热器，氧加热器，氧气净化器，第一冷水机组、第二冷水机组，氧气纯化器，其中氧自过热器的氧气输入端连接于电解水制氢系统的氧气输出端，氧自过热器的氧气输出端连接于氧加热器的氧气输入端，氧加热器的氧气输出端连接于氧气净化器的氧气输入端，氧气净化器的净化氧气输出端连接于第一冷水机组和第二冷水机组的氧气输入端，冷水机组和冷水机组的氧气输出端连接于氧气纯化器的氧气输入端，氧气纯化器输出端纯化后氧气通过管道送入换热系统，所述换热系统包括换热器和过冷器，所述液氧存储系统包括液氧贮槽，所述空分压缩及膨胀系统包括增压机，用于获得压缩气体；至少一台膨胀机，该膨胀机含膨胀机增压端、冷却器、膨胀机膨胀端；流程液氧泵和液氧增压泵，所述液氧存储系统的输出端连接于液氧增压泵的输入端，液氧增压泵的输出端连接于流程液氧泵的输入端，所述换热系统及空分压缩及膨胀系统与空分精馏系统高度耦合，其中所述换热器设置至少四个正流通道和二个通道，四个正流通道分别为纯化后氧气通道、带压空气通道、增压后气体通道和增压膨胀气体通道，二个返流通道分别为高压氧气产品通道、返流气体通道，所述换热器的纯化后氧气通道输入端连接于氧气纯化器的氧气输出端，换热器的纯化后氧气通道输出端连接于阀的输入端，阀的输出端连接于过冷器的热流体输入端，过冷器的热流体输出端的液氧经阀门和管道连接于液氧存储系统的输入端，换热器的带压空气通道输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，换热器的带压空气通道输出端连接于空分精馏系统，换热器的增压后气体通道输入端连接于增压机的末级输出端，换热器的增压后气体通道输出端连接于节流阀的输入端；换热器的增压膨胀气体通道输入端连接于膨胀机增压端后冷却器输出端，换热器的增压膨胀气体通道输出端连接于膨胀机膨胀端的输入端，膨胀机膨胀端的输出端连接于空分精馏系统；换热器的高压氧气产品通道输入端连接于流程液氧泵的输出端，换热器的高压氧气产品通道输出端连接于高压氧气产品输出管道；换热器的返流通道输入端连接于过冷器的冷流体输出端，换热器的返流通道输出端连接于空分设备后续工艺，过冷器的冷流体输入端连接于空分精馏系统，所述增压机的输入端引入经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气，增压机的一段输出端连接于膨胀机增压端的输入端。
2.根据权利要求1所述利用绿电电解水制氢副产氧气的装置，其特征在于：所述空分精馏系统至少包括二个输入通道和二个输出通道，其中二个输入通道分别为高压气体节流输入通道、带压气体输入通道；二个输出通道分别为返流气体输出通道、流程液氧输出通道，该高压气体节流输入通道输入端连接于节流阀的输出端，带压气体输入通道输入端连接于换热器的带压空气通道输出端；返流气体输出通道连接于过冷器的冷流体输入端，流程液氧输出通道连接于阀的输出端，并连接于流程液氧泵的输入端。
3.根据权利要求2所述利用绿电电解水制氢副产氧气的装置，其特征在于：所述换热器在绿电充足时，该净化氧气送入换热器中进行换热液化后得到液氧，此液氧经阀后部分液氧耦合空分精馏系统精馏产生的液氧进入液程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气，其余部分液氧经过冷器过冷后进入液氧贮槽，当换热器在绿电不充足时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧和与净化氧气送入换热器中进行换热液化后得到的全部液氧一起进入流程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气，当换热器在绿电不工作时，液氧贮槽中的液氧经液氧增压泵增压后，与从空分精馏系统精馏产生的液氧一起进入流程液氧泵加压后，通过换热器和空分压缩及膨胀系统获得带压氧气。
4.根据权利要求3所述利用绿电电解水制氢副产氧气的装置，其特征在于：所述换热器为板翅式换热器。
5.根据权利要求1-4任意一项所述利用绿电电解水制氢副产氧气装置的使用方法，其特征在于：包括以下步骤：
步骤1：出绿色电解水制氢装置的副产氧气进入到氧自过热器中，被预加热至一定温度，当温度满足进入氧纯化器时，通过管道直接进入到氧纯化器中，当氧自过热温度不满足进入氧纯化器的要求时，则先进入氧加热器进行加热，加热后进入到氧纯化器中；加热后的氧气在氧纯化器中发生化学反应，将氧气中的杂质H2转化为H2O，CO转化为CO2；反应结束后的氧气进入到氧自过热器的热端，与出电解水制氢装置的副产氧气进行热交换降温，并通过经冷却机组冷却后继续降温，在此过程中将底部冷凝下来的水直接排空，冷却后的气体进入到氧净化器中除去氧气中的杂质；
步骤2：净化后的氧气进入到换热器中，在换热器中与返流气体和流程流氧进行换热，使净化氧气被冷却到液态，经阀后得到液氧，在绿电充足时，这部分液氧分为两股，其中一股液氧与从空分精馏系统精馏产生的液氧汇合进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体正流体进行汽化复热，得到带压氧气，另一股液氧经过冷器过冷后进入液氧贮槽贮存备用，在绿电不充足时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧和与净化氧气送入换热器中进行换热液化后得到的阀后的全部液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体正流体进行汽化复热，得到带压氧气，在绿电不工作时，贮存在液氧贮槽中的液氧经液氧增压泵增压后，补充从空分精馏系统精馏产生的液氧，一起进入流程液氧泵加压，加压后进入换热器，与纯化后氧气、增压后气体和增压膨胀气体正流体进行汽化复热，得到带压氧气；
步骤3：经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气的部分或全部进入增压机压缩，增压后一部分增压空气进入膨胀机增压端增压，增压后进入冷却器冷却后进入换热器；增压后另一部分直接进入换热器，进入换热器增压膨胀气体通道的空气从换热器中部抽出后进入膨胀机膨胀端膨胀，膨胀后进入空分精馏系统参与精馏，进入换热器增压后气体通道的空气被返流的流程液氧和从空分精馏系统中来的返流气体换热，冷却后从换热器底部抽出，经节流降压后进入空分精馏系统参与精馏，经空压机压缩、预冷系统预冷和分子筛系统纯化后的干净干燥的带压空气也可部分进入换热器的带压空气通道，被换热冷却后从换热器底部抽出，进入空分精馏系统参与精馏。
6.根据权利要求5所述的利用绿电电解水制氢副产氧气装置的使用方法，其特征在于：所述氧纯化器中使用的催化剂活性组分为钯、铂、铈金属及其氧化物中的一种或几种。
7.根据权利要求5所述的利用绿电电解水制氢副产氧气装置的使用方法，其特征在于：所述氧净化器中使用的净化剂为氧化铝和分子筛；其催化剂的填装方式为规整填料。
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